Device modified substrate article and methods for making

ABSTRACT

A method of making a device substrate article having a device modified substrate supported on a glass carrier substrate, including:
         treating at least a portion of the first surface of a device substrate, at least a portion of a first surface of a glass carrier, or a combination thereof, wherein the treating produces a surface having:
           silicon; oxygen; carbon; and fluorine amounts; and a metal to fluorine ratio as defined herein;   
           contacting the treated surface with an untreated or like-treated counterpart device substrate or glass carrier substrate to form a laminate comprised of the device substrate bonded to the glass carrier substrate;   modifying at least a portion of the non-bonded second surface of the device substrate of the laminate with at least one device surface modification treatment; and   separating the device substrate having the device modified second surface from the glass carrier substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation application of U.S. application Ser. No.15/302,098, filed Oct. 5, 2016, which claims the benefit of priority toU.S. Patent Application No. 61/977,364, filed on Apr. 9, 2014, entitledDEVICE MODIFIED SUBSTRATE ARTICLE AND METHODS FOR MAKING, the content ofwhich is incorporated herein by reference in its entirety.

This application is related to, but does not claim priority to, commonlyowned and assigned patent Applications: U.S. Ser. No. 61/596,727, filedFeb. 8, 2012, entitled “PROCESSING FLEXIBLE GLASS WITH A CARRIER”; U.S.Ser. No. 14/053,093, filed Oct. 14, 2013, entitled “ARTICLES WITHLOW-ELASTIC MODULUS LAYER AND RETAINED STRENGTH”; U.S. Ser. No.14/053,139, filed Oct. 14, 2013, entitled “LAMINATE ARTICLES WITHMODERATE ADHESION AND RETAINED STRENGTH”; U.S. Ser. No. 61/736,880,filed Dec. 13, 2012, entitled “FACILITATED PROCESSING FOR CONTROLLINGBONDING BETWEEN SHEET AND CARRIER”; and U.S. Ser. No. 61/736,887, filedDec. 12, 2012, entitled “GLASS AND METHODS OF MAKING GLASS ARTICLES.”

This application is related to, but does not claim priority to, U.S.Ser. No. 14/248,868, filed on Apr. 9, 2014 entitled “GLASS ARTICLESHAVING FILMS WITH MODERATE ADHESION AND RETAINED STRENGTH.”

The entire disclosure of any publication or patent document mentionedherein is entirely incorporated by reference.

BACKGROUND

The disclosure relates to a laminate article, the manufacture and use ofthe laminate article, and a glass sheet article or non-glass sheetarticle having a device modified surface for use in or as, for example,an electrical or an electronic device. Additionally, the disclosurerelates to a method for bonding and debonding a glass sheet article ornon-glass sheet article and a carrier substrate.

SUMMARY

In embodiments, the disclosure provides a glass device substrate ornon-glass device substrate having a device modified surface.

In embodiments, the disclosure provides a laminate article comprising aglass device substrate work piece reversibly bonded to a reusablecarrier, the laminate having a silicon and oxygen depleted and fluorineand carbon enriched glass surface at the interface.

In embodiments, the disclosure provides a method for bonding anddebonding a laminate comprising a glass device substrate work piece anda carrier substrate for the work piece.

In embodiments, the disclosure provides a method for forming a moderateor intermediate strength bond or adhesion between a carrier and a thinglass device substrate to create a temporary bond, which temporary bondis sufficiently strong to survive, for example, thin film transistors(TFT) processing, but the bond is sufficiently weak to permit timelydebonding or separation of the carrier substrate and the glass devicesubstrate after surface processing of the device substrate is completed.The intermediate strength bond or moderate bonding property enables are-usable carrier function and manufacturing cycle. The moderate bondingproperty can be, for example, in one or more portions of the areabetween the carrier substrate and the device substrate work piece, orthe entire area between the carrier substrate and the device substratework piece.

BRIEF DESCRIPTION OF THE DRAWINGS

In embodiments of the disclosure:

FIG. 1 shows a schematic of the disclosed reusable carrier process(100).

FIGS. 2A and 2B show the change in contact angle (FIG. 2A) and surfaceenergy (FIG. 2B) for CF₄ and CHF₃ plasma polymer treated glass surfaces.

FIGS. 3A and 3B show surface concentrations of fluorine (310) and carbon(320) and oxygen (330), (FIG. 3A) as measured by XPS and theconcentration of inorganic fluorine atoms (bonded to metal) (340) andthe concentration of organic fluorine atoms (in fluoropolymer) (350)(FIG. 3B) as measured by XPS for fluorocarbon plasma treated glasssurfaces treated with different mol fractions of CF₄ and CHF₃.

FIG. 4 shows changes in the glass surface elemental composition inatomic % as measured by XPS with increasing polymer forming plasmatreatment times for separate CHF₃ or CF₄ plasma treatments.

FIGS. 5A to 5B show the change in adhesion or bond energy as a functionof the anneal temperature (FIG. 5A) and anneal time (FIG. 5B) forselected surface treatments.

FIG. 6 is a top view of a thin sheet and carrier, having interposers.

FIG. 7 is a cross-sectional view of the thin sheet and carrier as takenalong line 7-7 of FIG. 6.

FIG. 8 is a cross-sectional view, similar to that in FIG. 20, but havingadditional devices disposed on the thin sheet.

DETAILED DESCRIPTION

Various embodiments of the disclosure will be described in detail withreference to drawings, if any. Reference to various embodiments does notlimit the scope of the invention, which is limited only by the scope ofthe claims attached hereto. Additionally, any examples set forth in thisspecification are not limiting and merely set forth some of the manypossible embodiments of the claimed invention. Definitions

“At %,” “at %,” or like refer to atom or atomic percentage.

“Temporary bond” refers to a non-destructive and reversible adhesionbetween a glass device substrate and the carrier substrate of thedisclosed laminate, which bond is sufficient to survive further surfacemodification processing, but which bond can be disrupted with, forexample, a mechanical force to permit separation of the processed thinglass device substrate and the carrier substrate.

“Thin glass device substrate” refers to, for example, Corning® Willow®glass, and having thicknesses as defined herein.

“Include,” “includes,” or like terms means encompassing but not limitedto, that is, inclusive and not exclusive.

“About” modifying, for example, the quantity of an ingredient in acomposition, concentrations, volumes, process temperature, process time,yields, flow rates, pressures, viscosities, and like values, and rangesthereof, or a dimension of a component, and like values, and rangesthereof, employed in describing the embodiments of the disclosure,refers to variation in the numerical quantity that can occur, forexample: through typical measuring and handling procedures used forpreparing materials, compositions, composites, concentrates, componentparts, articles of manufacture, or use formulations; through inadvertenterror in these procedures; through differences in the manufacture,source, or purity of starting materials or ingredients used to carry outthe methods; and like considerations. The term “about” also encompassesamounts that differ due to aging of a composition or formulation with aparticular initial concentration or mixture, and amounts that differ dueto mixing or processing a composition or formulation with a particularinitial concentration or mixture.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

The indefinite article “a” or “an” and its corresponding definitearticle “the” as used herein means at least one, or one or more, unlessspecified otherwise.

Abbreviations, which are well known to one of ordinary skill in the art,may be used (e.g., “h” or “hrs” for hour or hours, “g” or “gm” forgram(s), “mL” for milliliters, and “rt” for room temperature, “nm” fornanometers, and like abbreviations).

Specific and preferred values disclosed for components, ingredients,additives, dimensions, conditions, times, and like aspects, and rangesthereof, are for illustration only; they do not exclude other definedvalues or other values within defined ranges. The apparatus and methodsof the disclosure can include any value or any combination of thevalues, specific values, more specific values, and preferred valuesdescribed herein, including explicit or implicit intermediate values andranges.

In embodiments, the disclosure provides a method of forming a temporarybond by surface modification, which surface modification createsmoderate or intermediate adhesion between at least a portion of thesurface of a work piece substrate and at least a portion of the surfaceof the glass carrier substrate to produce a laminate for use in making adevice modified substrate from the work piece substrate.

The temporary bonding condition in the laminate eliminates waste and canreduce manufacturing costs by permitting manufacturers to re-use thecarrier member for device fabrication on the thin glass sheet asschematically shown in FIG. 1.

In embodiments, the disclosure provides a method of making a laminatearticle that includes: forming a temporary bond between at least aportion of a work piece, such as a glass sheet, a glass substrate, or anon-glass substrate (e.g., a flexible glass sheet or silicon wafer), anda glass carrier substrate.

Forming the temporary bond can be accomplished by, for example, treatingto effect a surface modification, which surface modification createsmoderate adhesion between the work piece and the carrier substrate.

The intermediate or moderate adhesion can be achieved by depletion ofthe surface layer of silicon and oxygen atoms and the enrichment of thesurface layer of fluorine and carbon atoms. The depletion of siliconatoms also leads to a relative enrichment of other cations in glass workpiece or carrier substrate, which other cations are not depleted withthe silicon atoms. For example, depletion of silicon atoms such as insilica in the treated surface layer leads to a relative enrichment inalumina and alkaline earth atoms. In embodiments, the modified surfacecan be formed by, for example, an etch process. However, the depositionor etch processes can deplete a glass work piece's surface of silica,boron, and other glass components, and consequently can enrich the glasswork piece's surface in alkaline earths and fluorine reaction productsin a relative sense.

The surface energy of the modified surface is adjustable between, forexample, Teflon® and glass depending on the relative ratio of etch gasto polymer former. In a preferred embodiment, exposure to a plasmacontaining a high ratio of etch gas to polymer former can create ahighly polar surface having a sparse coverage of carbon based polymerson a modified glass surface where most metal to oxygen bonds have beenreplaced by metal to fluorine bonds. This highly polar surface exhibitsa high energy surface which readily bonds with glass provided that thesurface roughness is small, for example, below about 2 nm. The temporarybonding preferably is strong enough to survive flat panel display (FPD)processing, including, for example, wet ultrasonic, vacuum, and thermalprocesses, and remain de-bondable by application of a sufficient peelingforce. De-bonding permits disintegration of the laminate, that isseparation of the glass carrier substrate from the processed thin glasssheet having, for example, devices or structure on the surface of thethin glass sheet resulting from intermediate processing. The separatedglass carrier, if desired, can be repeatedly re-used in numerous cyclesof the disclosed method.

In embodiments, the disclosed method uses moderate bonding of a flexibleglass sheet (i.e., a work piece) to the glass carrier, which moderatebonding permits the subsequent removal of the thin glass sheet from thecarriers to provide re-usable carrier.

The disclosed method is advantaged in several respects, including, forexample:

-   -   eliminating an air gap between the flexible glass sheet and the        glass carrier substrate, which air gap is disclosed in prior        methods, to provide greater manufacturing reliability in vacuum,        ultrasonic, and wet processing;    -   providing a flexible, thin, or like glass sheet, or non-glass        sheet, work piece having a flatter facial work surface that can        improve an user's latitude in circuit or device construction on        the work piece and processing (e.g., lithography) by reducing        the height variation within the laminate;    -   providing simpler bonding surface preparation and bonding        surface processing;    -   providing easier de-bonding or separation of the work piece from        the carrier substrate;    -   providing a reusable carrier substrates; and    -   providing a bonding surface between the work piece and the        carrier substrate that offers higher thermal stability than        commercially available polymer wafer bonding approaches.

In embodiments, the disclosed flexible substrates offer an opportunitiesfor less costly manufacturing of devices using, for example,roll-to-roll processing, and the potential to make thinner, lighter,more flexible and durable displays. However, the technology, equipment,and processes required for roll-to-roll processing of high qualitydisplays are not yet fully developed. Since panel makers have alreadyheavily invested in toolsets to process large sheets of glass,laminating a flexible substrate to a carrier substrate and makingdisplay devices by a sheet-to-sheet process offers a shorter termsolution to develop the value proposition of thinner, lighter, and moreflexible displays. Displays have been demonstrated on polymer sheetssuch as polyethylene naphthalate (PEN) where the device fabrication wassheet-to-sheet with the PEN laminated to a glass carrier. The uppertemperature limit of the PEN limits the device quality and processesthat can be used. In addition, the high permeability of the polymersubstrate leads to environmental degradation of OLED devices where anear hermetic package is typically required. Thin film encapsulationoffers promise potential solution to overcome this limitation, but theencapsulation approach has not yet been demonstrated to provideacceptable yields for large volumes.

In a similar manner, display devices can be manufactured using a glasscarrier substrate that has been laminated to one or more flexible glasssubstrates. It is anticipated that the low permeability and improvedtemperature and chemical resistance of the flexible glass substrate willenable higher performance, longer lifetime, and flexible displays.

The above mentioned commonly owned and assigned U.S. Ser. No. 61/596,727mentions bonding a thin sheet, for example, a flexible glass sheet, to acarrier initially by van der Waals forces, then increasing the bondstrength in certain regions while retaining the ability to remove thethin sheet after processing the thin sheet or carrier to form devicesthereon, for example, electronic or display devices, components ofelectronic or display devices, OLED materials, photo-voltaic (PV)structures, or thin film transistors. At least a portion of the thinglass is bonded to a carrier substrate such that there is preventeddevice process fluids from entering between the thin sheet and carrier,where there is provided a reduced possibility of contaminatingdownstream processes, i.e., the bonded seal between the thin sheet andcarrier is hermetic, and in some preferred embodiments, this sealencompasses the outside of the article thereby preventing liquid or gasintrusion into or out of any region of the sealed article.

JP2013184346 and WO2013179881, assigned to Asahi, mention a peelableglass laminated body having a support substrate with a first inorganiclayer, and a glass substrate with an inorganic layer provided with asecond inorganic layer, either or both of the first and second inorganiclayers contain at least one of: a metal oxide, metal nitride, a metaloxynitride, metal carbide, a metal carbonitride, a metal silicide, or ametal fluoride.

In low temperature polysilicone (LTPS) device fabrication processes,temperatures approaching 600° C. or greater, vacuum, and wet etchenvironments may be used. These conditions limit the materials that maybe used, and place significant stability demands on the laminate'scomponents comprised of a carrier substrate and a sheet substrate.

In embodiments, the disclosure provides a method for bonding a flexibleglass sheet to a carrier substrate to form a laminate, processing thelaminate, such as creating a circuit or device on the outer unbondedsurface of the flexible glass sheet, and debonding the flexible glasssheet from a carrier. The method can use existing capitalinfrastructure, enables processing of thin flexible glass, for example,glass having a thickness less than or equal to 0.3 mm thick, withoutcontamination or loss of bond strength between the thin flexible glassand carrier substrate at higher processing temperatures, and theresulting surface or device modified thin flexible glass de-bonds easilyfrom the carrier substrate at the end of the process.

In embodiments, the disclosure provides a method having considerableoperational flexibility, including for example: cleaning and surfacepreparation of the flexible glass sheet and carrier substrate tofacilitate bonding; maintaining adequate bond strength between theflexible sheet and the carrier substrate at the bonded area; maintainingreleasability of the flexible sheet from the carrier substrate; andoptionally cleaning the separated carrier substrate for reuse in themethod.

In embodiments, in the glass-to-glass bonding process, the work-pieceand carrier substrate glass surfaces can be cleaned prior to laminatejoining to remove all extraneous metal, organic, and particulateresidues, and to leave a mostly silanol terminated contact surface.

If the glass contact surfaces are first brought into intimate contact,where van der Waals forces pull them together, with heat and optionallypressure, the surface silanol groups can condense to form strong Si—O—Sibonds across the interface between the opposing glass surfaces topermanently fuse the opposing glass pieces causing the opposing piecesinseparable without breakage. Metal, organic, and particulate residuecan be used to prevent or limit bonding of the opposing glass pieces byobscuring at least one glass surface and preventing intimate contact,which obscuration may be called for to further moderate bonding betweenthe work-piece substrate and carrier substrate glass.

A high silanol surface concentration can form an undesirably strong bondbetween the opposing glass pieces. The number of bonds per unit areawill be determined by the probability of two silanol species on opposingsurfaces reacting to condense out water. Zhuravlev has reported theaverage number of hydroxyls per nm² for well hydrated silica as from 4.6to 4.9. (see Zhuravlev, L. T., The Surface Chemistry of AmorphousSilika, Zhuravlev Model, Colloids and Surfaces A: PhysiochemicalEngineering Aspects, 173 (2000) 1-38).

In the abovementioned U.S. Ser. No. 61/596,727, a non-bonding region isformed within a bonded periphery, and the primary means described forforming such non-bonding area is increasing surface roughness. Aroughness of greater than 2 nm Ra is called for to prevent opposingglass-to-glass bonds from forming during the elevated temperature phaseof the bonding process. In U.S. Ser. No. 61/736,880 a non-bonding areais formed by weakening the van der Waals bonding between carrier andthin glass.

Thermal, vacuum, solvent, acidic, and ultrasonic flat panel display(FPD) processes require a robust bond between the thin flexible glassbound to a carrier.

Three transistor technologies are used in mass production for FPDbackplane fabrication, including: amorphous silicon (aSi) bottom gateTFT; polycrystalline silicon (pSi) top gate TFT; and amorphous oxide(IGZO) bottom gate TFT. The general process begins with cleaning of aglass substrate, typically in hot alkaline solutions with ultrasonic ormegasonic agitation, followed by DI water rinse.

The device structure can be fabricated in a number of subtractive cyclesof material deposition and photolithographic patterning followed bymaterial etching. Metal, dielectric, and semiconductor materials can bedeposited by vacuum processes (e.g., sputtering metals, transparentconductive oxides and oxide semiconductors, Chemical Vapor Deposition(CVD) deposition of amorphous silicon, silicon nitride, and silicondioxide at elevated temperature, 150 to 450° C.). Other thermal processsteps can include, for example, up to 600° C. p-Si crystallization, 350to 450° C. oxide semiconductor annealing, up to 650° C. dopantannealing, and about 200 to 350° C. contact annealing. Layers can bepatterned by a photolithographic patterning of a polymer resist,etching, and followed by resist strip. Both vacuum plasma (dry) etch andacidic wet etch processes can be used. In FPD processing, thephotoresist is typically stripped by a hot solvent and, for example,along with ultrasonic or megasonic agitation.

Adhesive wafer bonding has been widely used in microelectromechanicalsystems (MEMS) and semiconductor processing for back end steps whereprocesses are less harsh.

Commercial adhesives by Brewer Science and Henkel are typically thickpolymer adhesive layers of about 5 to 200 microns. The large thicknessof these layers can create the potential for large amounts of volatiles,trapped solvents, and adsorbed species to contaminate FPD processes.These materials can thermally decompose and outgas above about 250° C.The materials can also cause contamination in downstream steps by actingas a sink for gases, solvents, and acids, which can outgas in subsequentprocesses or process steps.

An overly strong covalent bond between the thin glass work piece and theglass carrier can preclude complete separation and re-usability of thecarrier.

In the abovementioned U.S. Ser. No. 61/596,727 applicant demonstratedFPD by the formation of a strong covalent bond around the periphery of athin glass sheet bound to a carrier, and that the thin glass sheet boundto the carrier was durable enough to survive FPD processing. However,the carriers were not reusable. The periphery was permanently bonded bycovalent Si—O—Si bonding with an adhesive force of about 2000 mJ/m²,which is on the order of the fracture strength of the glass, which isapproximately 2500 mJ/m². Prying or peeling cannot be used to separateflexible glass piece and carrier. Instead, the non-bonded center withthe surface constructed devices is scribed and extracted leaving asscrap a bonded periphery on the carrier.

Although not being bound by theory, surface adhesion theory has beenextensively studied and articulated (see “A theory for the estimation ofsurface and interfacial energies. I. derivation and application tointerfacial tension”, L. A. Girifalco and R. J. Good, J. Phys. Chem.,61, 904 (1957)).

In U.S. Ser. No. 61/736,887 it was demonstrated that thin plasmafluoropolymer surface treatments can vary the surface energy of glassbetween that of Teflon® and water.

This precise control of both Van der Waal and covalent interactions attheir fractional values via surface modification to achieve desiredadhesion energy is an aspect of the present disclosure.

In embodiments, the disclosure provides a method of making a devicemodified substrate supported on a glass carrier substrate, comprising:

-   -   treating at least a portion of the first surface of a glass        device substrate, at least a portion of a first surface of a        glass carrier substrate, or a combination thereof, wherein the        treated glass surface has:        -   silicon of about 0.1 to about 14 at %;        -   oxygen of about 1 to about 40 at %;        -   carbon of about 3 to 60 at %;        -   fluorine of about 5 to 65 at %; and        -   a metal to fluorine (M:F) atomic ratio of about 1:1 to about            1:3;    -   contacting the treated glass surface with an untreated or a        like-treated counterpart glass device substrate or glass carrier        substrate to form a laminate comprised of the glass device        substrate bonded to the glass carrier substrate;    -   modifying at least a portion of the non-bonded second surface of        the glass device substrate of the laminate with at least one        device surface modification treatment; and    -   optionally separating the glass device substrate having the        device modified second surface from the glass carrier substrate.

In embodiments, when the device modified substrate is a glass, forexample, Corning® Eagle XG® (“EXG”), the treated surface or interfacecan preferably have:

-   -   silicon of about 2 to about 9 at %;    -   oxygen of about 7 to about 14 at %;    -   carbon of about 4 to 10 at %; and    -   fluorine of about 45 to 60 at %, as measured by XPS.

The measured atomic % can vary depending upon the surface measurementmethod selected, for example, XPS or ESCA can probe the outer most 10 nmof the surface, such as 2 to 6 nm.

In embodiments, the method can further comprise heating the laminate inat least one device surface modification treatment at from about 200 toabout 700° C., for 1 second to 1200 minutes.

In embodiments, treating can include or comprise, for example:contacting at least one portion of the glass surface with a fluorocarbonplasma comprised of polymerizing agents or etching agents, or acombination thereof.

In embodiments, the polymerizing agents can include or comprise, forexample, at least one of CHF₃, C₄F₈, C₃F₆, C₃F₈, H₂, CH₄, a hydrocarbonhaving from 3 to 12 carbon atoms and free of fluorine atoms selectedfrom the group consisting of an alkane, an alkenes, an alkyl, anaromatic, or a combination thereof, and the etching agents comprise atleast one of CF₄, C₂F₆, NF₃, SF₆, HF, or a combination thereof.

In embodiments, the laminate can have an interfacial bond with anadhesive strength of from about 100 to about 2,000 mJ/m² between theglass device substrate and the glass carrier substrate.

In embodiments, treating can be accomplished, for example, on both ofthe glass device substrate and the glass carrier substrate, oralternatively, accomplished on only one of the glass device substrate orthe glass carrier substrate.

In embodiments, the glass device substrate can have a thickness of, forexample, from about 10 to about 500 microns, the carrier glass substratehas a thickness of, for example, about 200 microns to 3 mm, and thethickness of the interfacial bonding layer between the glass devicesubstrate and the glass carrier substrate of, for example, from about asingle atomic layer to about 100 nanometer.

In embodiments, modifying with at least one device surface modificationtreatment is selected from, for example, at least one of: etching,coating, printing, plating, vapor deposition, sputtering, and likemodifying treatments, or combinations thereof.

In embodiments, separating can be, for example, at least one of:

-   -   peeling the device surface modified glass device substrate from        the glass carrier substrate, peeling the glass carrier substrate        from the glass device substrate, or both; and    -   contacting at least one of the glass device substrate or the        glass carrier substrate with a suction device, a gripper device,        a knife edge, or a combination thereof.

In embodiments, the method can further comprise, for example, cleaningthe separated glass carrier substrate for repeated reuse in the method.

In embodiments, the glass carrier substrate, the glass device substrate,or both, can be, for example, flexible, rigid, or have an intermediateflexibility or rigidity.

In embodiments, the disclosure provides a laminate glass article,comprising:

-   -   a glass device substrate bonded to a glass carrier substrate        with at least one bonded surface that has been treated with a        plasma selected from:    -   a fluoropolymer;    -   the reaction products of a fluorinated etching agent;    -   or a combination thereof,        wherein the interfacial bond strength between the glass device        substrate and the carrier glass substrate is from about 100 to        about 1,000 mJ/m², the interface between the glass device        substrate and the glass carrier has a silicon content of from        about 1 to about 14 at %; a fluorine content of from about 5 to        60 at %, and the interface between the glass device substrate        and the glass carrier substrate has a metal to fluorine (M:F)        atomic ratio of about 1:1 to 1:3.

In embodiments, the glass device substrate or device modified substratehas a facial contact area that is smaller than, larger than, or the samesize, compared to the facial contact area of the glass carriersubstrate.

In embodiments, the article can further comprise, for example, thenon-bonded second surface of the glass device substrate in the laminatearticle having at least one device modified surface area.

In embodiments, the glass device substrate can have a thickness of fromabout 20 to about 500 microns, the carrier glass substrate has athickness of about 200 microns to about 3 mm, and the thickness of theinterfacial bonding layer between the glass device substrate and theglass carrier substrate can be, for example, from about a single atomiclayer to about 100 nanometer.

In embodiments, the disclosure provides a method of making a laminatearticle comprising a device substrate having a device modifiedsemiconductor substrate supported on a glass carrier substrate, themethod comprising:

-   -   treating at least a portion of a first surface of the glass        carrier substrate, wherein the treated first surface has:        -   silicon of about 0.1 to about 14 at %;        -   oxygen of about 1 to about 40 at %;        -   carbon of about 3 to 60 at %;        -   fluorine of about 5 to 65 at %; and        -   a metal to fluorine (M:F) atomic ratio of about 1:1 to about            1:3; and    -   contacting the treated first surface with the device        semiconductor substrate to form a laminate comprised of the        device semiconductor substrate bonded to the treated first        surface of the glass carrier substrate;    -   modifying at least a portion of the non-bonded second surface of        the device semiconductor substrate of the laminate with at least        one device surface modification treatment; and    -   optionally separating the device semiconductor substrate having        the device modified second surface from the glass carrier        substrate.

In embodiments, the glass device substrate can have a thickness of fromabout 20 to about 500 microns, the carrier glass substrate has athickness of about 200 microns to about 3 mm, and the thickness of theinterfacial bonding layer between the glass device substrate and theglass carrier substrate can be, for example, from about a single atomiclayer to about 100 nanometer.

In embodiments, the method can further comprise, for example, heatingthe laminate in at least one device surface modification treatment atfrom about 200 to about 700° C., for 1 second to 1200 minutes.

In embodiments, treating can comprise: contacting the glass surface witha fluorocarbon plasma comprised of a polymerizing agent, an etchingagent, or a combination thereof; and

-   -   the device substrate is selected from a silicon (Si), a gallium        arsenide (GaAs), or a combination substrate.

In embodiments, the polymerizing agent can be, for example, at least oneof CHF₃, C₃F₈, C₃F₆, H₂, CH₄, a hydrocarbon having from 3 to 12 carbonatoms and free of fluorine atoms selected from the group consisting ofhydrocarbyl moieties, such as an alkane, an alkene, an alkyl, anaromatic, or a combination thereof; and the etching agent comprise atleast one of CF₄, C₂F₆, NF₃, SF₆, HF, or a combination thereof.

In embodiments, the laminate can have an interfacial bond with anadhesive strength of from about 100 to about 1,000 mJ/m² between thedevice semiconductor substrate and the glass carrier substrate.

In embodiments, the device semiconductor substrate has a thickness offrom about 20 to about 1000 microns, the carrier glass substrate has athickness of about 200 microns to 3 mm, and the thickness of theinterfacial bonding layer between the device semiconductor substrate andthe glass carrier substrate is from about a single atomic layer to about100 nanometer.

In embodiments, modifying with at least one device surface modificationtreatment can be, for example, at least one of: etching, coating,printing, plating, vapor deposition, sputtering, or combinationsthereof.

In embodiments, the method of making a device semiconductor substratecan further include, for example, cleaning the separated glass carriersubstrate for repeated reuse in the method.

In embodiments, the glass carrier substrate can be, for example,flexible, rigid, or can have an intermediate flexibility or rigidity.

In embodiments, the device substrate can be, for example, flexible,rigid, or has an intermediate flexibility or rigidity.

In embodiments, the laminate glass article, can include, for example:

-   -   a device semiconductor substrate bonded to a glass carrier        substrate, the bond comprising the glass carrier having a        surface modified by plasma treatment for from at least one of        the following: a fluoropolymer; the reaction products of the        fluorinated etching agents, with the glass substrate; or a        combination thereof,        wherein the interfacial bond strength between the device        semiconductor substrate and the carrier glass substrate is from        about 100 to about 1,000 mJ/m², the interface between the device        semiconductor substrate and the glass carrier has silicon        content of from about 0.1 to about 14 at %; a fluorine content        of from about 5 to 60 at %, and the interface between the        flexible glass sheet article and the glass carrier has a metal        to fluorine (M:F) atomic ratio of about 1:1 to 1:3.

In embodiments, the device semiconductor substrate has a facial contactarea that is smaller than, larger than, or the same size, compared tothe facial contact area of the glass carrier substrate.

In embodiments, the article can further comprise the non-bonded secondsurface of the device semiconductor substrate in the laminate having atleast one device modified surface.

In embodiments, the device semiconductor substrate has a thickness offrom about 20 to about 1000 microns, the carrier glass substrate has athickness of about 200 microns to about 3 mm, and the thickness of theinterfacial bonding layer between the device semiconductor substrate andthe glass carrier substrate can be, for example, from about a singleatomic layer to about 100 nanometer.

Referring to the Figures, FIG. 1 shows a schematic of the disclosedreusable carrier process (100). The reusable process (100) can include,for example, a carrier cleaning or pre-conditioning step (110) where acarrier substrate (105) substrate, such as a new (105) or re-used (140)substrate, is subjected to cleaning (110) to produce the cleaned orpre-conditioned carrier (105 or 140). The carrier (105) can be, forexample, a sheet or roll stock made of glass, ceramic, and likematerials, or a combination of materials. The resulting carrier (105 or140) can be subjected to the disclosed adhesive surface conditioning oran adhesive surface treatment (115) to, for example, deposit an adhesivelayer with extended treatments, or more preferably with shortertreatments, create a chemically altered interface (117) on the treatedcarrier (106). The adhesive treatment can be, for example, an additiveplasma fluoropolymer treatment, a subtractive etchant treatment, or acombination thereof, as described herein. Next, the carrier (106) havingthe adhesive conditioned surface treatment (117) receives a work piece(122), such as a flexible glass sheet, in a bonding or combination (120)step to provide a laminate. The adhesive conditioning or surfacetreatment can include heating the conditioned surface (117), the carrier(106), or both, with or without the work piece (122) present. Thelaminate comprised of the bonded or combined work piece (122) and thecarrier (106), can be subjected to, for example, one or more devicesurface modification step or steps (125), which modifies the exteriorwork surface of the flexible glass sheet work piece (122), that is, onthe surface of the work piece which is not facing or is not in directcontact with the carrier (106) or not in direct contact with theinterfacial adhesive layer (117), to provide the laminate having anexterior surface modification comprising the combined work piece (122)and carrier (106) having a device modified work surface (127) on thework piece (122). Device or work surface modification can include any ofone or more compatible steps, for example, additive processing,subtractive processing, or combinations thereof, that substantivelychanges at least a portion of the work surface, for example, coating,deposition, controlled topological changes, scoring, cutting, drilling,machining, circuit creation, device creation, flat panel display (FPD)fabrication, and like surface modifications, or combinations thereof.The laminate comprising the combined work piece (122) and the carrier(106) having the modified work surface (127) can be separated orde-bonded (130) by any suitable means, method, or instrumentality, forexample, by a mechanical force or contact, such as with a knife edge orblade, suction cup or gripper, air knife, and like tools or techniques,to separate the work piece (135) such as a device surface modified glasssheet, from the carrier (106). The used carrier (140) can be cleaned toproduce a re-used carrier (105) described above, and the above describedprocess can be repeated continuously.

FIGS. 2A and 2B show the change in contact angle (FIG. 2A) and surfaceenergy (FIG. 2B) for CF4 and CHF3 plasma polymer treated glass surfaces.The contact angle measurements in FIG. 2A used different solvents (210,water; 215, diiodomethane; and 220, hexadecane). The surface energymeasurements in FIG. 2B used different energy metrics (230, total; 240,polar; and 250, dispersion; where total energy (230) is the sum of thepolar and the dispersion energies, i.e., “240+250”). The surface energyand the polar and dispersion components are measured by fitting the Wumodel (see S. Wu, J. Polym. Sci C 34, 19 (1971)) of solid-liquidinterfacial energy to three contact angles of three test liquids: water,diiodomethane, and hexadecane.

FIGS. 3A and 3B show surface concentrations of fluorine (310), carbon(320), and oxygen (330) (FIG. 3A), and concentration of fluorine atomsdue to metal fluorides (340) and concentration of fluorine atomsattributable to fluoropolymer (350) (FIG. 3B) as measured by XPS for CF₄and CHF₃ plasma fluoropolymer treated Eagle XG® glass surfaces havingdifferent mol fractions of CF₄ and CHF₃ in the plasma. The surfaceconcentration of fluorine varies little (e.g., 49 to 52 at %) across theCF₄ and CHF₃ gas mixture, while the carbon concentration decreases asCF₄ is added. The high fluorine concentration (49 to 52 at %) and lowoxygen (7.5 to 12 at %) is consistent with the CHF₃ and CF₄ plasmapolymer surface treatment forming a metal fluoride surface.

FIG. 4 shows the changes in elemental surface composition as measured byXPS as a function of different plasma treatment times. In each instance,the flow rate of the gas was 50 standard cubic centimeter per minute(sccm) at a pressure of 50 milli-torrs. The plasma treatment was eitherpure CHF₃ or pure CF₄ (400, 410, and 420 refer to 6 seconds, 60 seconds,and 600 seconds of CHF₃ plasma treatments, respectively, and 430, 440,and 450 refer to 6 seconds, 60 seconds, and 600 seconds of CF₄ plasmatreatment times, respectively). The surface composition of untreatedflat glass is also presented for comparison (460; negative control). Thedata shows that while for 6 seconds of plasma treatment, the surfaceconcentration of carbon is less than 10 at %, the surface concentrationof fluorine exceeds 40 at %.

FIG. 4 also shows that for CF₄ plasma polymer surface treatments thereis little increase in carbon or fluorine concentration after 6 seconds.Silicon, oxygen, and boron concentrations decrease with increasing CF₄plasma exposure time, while Al, Mg, Ca, and Sr concentrations increasewith increasing CF₄ plasma exposure time. This is consistent with CF₄plasma treatment etching the glass surface and depleting the surface ofsilicon, oxygen, and boron.

Changes in bond energy vs. anneal temperature and anneal time for CF₄and CHF₃ plasma polymer treated Eagle XG® carrier bonded to SC1 cleanedthin glass is shown in FIG. 5A, and SC1 treated Eagle XG® carrier to SC1treated thin glass is shown in FIG. 5B.

FIG. 5A shows the change in adhesion or bond energy as a function of theanneal temperature for RIE mode CF4 and CHF3 treated Eagle XG® carrierswith three different surface energies prepared by changing the gas ratioas described in FIG. 2: at 40 mJ/m² surface energy (510) the bond energyis too weak and is inadequate for surviving low temperature polysilicon(LTPS) processing. At 55 mJ/m² surface energy (511) the bond energy isadequate to survive LPTS processing; and at 72 mJ/m² the surface energy(512) is still adequate for surviving LTPS processing but is moredifficult to peel off the flexible glass sheet from the carrier. Thebond energy (SE) or adhesion limit (515) is about 2500 mJ per squaremeter where attempted separation results in glass breakage failure.

FIG. 5B shows the bond energy (SE) of an SC1 treated Eagle XG® carrierto SC1 treated thin glass or adhesion of a flexible glass sheet to thecarrier in the laminate as a function of anneal time at 100° C. (520),150° C. (521), 200° C. (522), 250° C. (523) and 300° C. (524). Bondenergy is observed to increase rapidly with increasing temperature. At300° C. (524), the thin glass was permanently bonded and could not beremoved without breakage at annealing times of 10 min and above.

Bond energy (BE) measurements were accomplished using the wedge testmethod (see Tong, Q. Y., et al. “Semiconductor Wafer Bonding”, Annu RevMater Sci, vol. 28, no. 1, pp. 215-241, 1998). The bond energy oradhesion between a surface treated carrier and a clean flexible glasscan be determined by inserting a thin blade and measuring the cracklength. The bond energy γ is related to the carrier Young's modulus E₁,carrier thickness t_(w1), flexible glass modulus E₂, flexible glassthickness t_(w2), blade thickness t_(b), and crack length L by theequation:

$\gamma = \frac{3\; t_{b}^{2}E_{1}t_{w\; 1}^{3}E_{2}t_{w\; 2}^{3}}{16\;{L^{4}\left( {{E_{1}t_{w\; 1}^{3}} + {E_{2}t_{w\; 2}^{3}}} \right)}}$

From the examples in FIG. 5A it can be seen that creating a silicon andoxygen depleted and fluorine and carbon enhanced surface rich inalkaline earth fluorides by an inhomogeneous etching of glass surfaceoptionally combined with polymer deposition can readily form temporaryremovable or releasable bonds to other high energy surfaces such asglass and in particular, thin glass.

In embodiments, a flexible glass sheet can have a thickness of fromabout 50 to about 300 microns, and a carrier glass article can have a ofabout 200 microns to 3 mm. Unexpectedly, this silicon and oxygendepleted and fluorine and carbon enriched surface does not permanentlybond to glass surfaces at temperatures below about 600° C.

The surface treatments described herein may be used to process thinwafers in semiconductor and/or interposer processing. Some examples ofthe present invention are generally directed to carriers bonded to andremoved from thinner substrates to allow processing of the thinnersubstrates. More particularly, some examples of the present inventionare directed to methods and apparatuses for bonding wafers to carriersfor semiconductor and/or interposer processing, and then debonding thewafers from the carriers after such processing.

Semiconductor devices are fabricated by forming active devices on orwithin a semiconductor wafer. The semiconductor wafer may comprise, forexample, glass, silicon, polysilicon, single crystal silicon, siliconoxide, aluminum oxide, combinations of these, and/or the like. Hundredsor thousands of integrated circuits (ICs) or dies are typicallymanufactured on a single wafer. Typically, a plurality of insulating,conductive, and semiconductive material layers are sequentiallydeposited and patterned over the wafer to form the ICs. One of theuppermost-formed material layers typically comprises a layer for bondpads which make electrical connection to the underlying active areas andcomponents within the wafer.

After the ICs are formed, the wafer may be subjected to backsideprocessing. The backside processing may include thinning the wafer toprepare the wafer for packaging. For example, in some technologies,backside processing may include forming electrical connections tothrough-substrate vias formed through the wafer for providing backsidecontacts. In this example, the backside of the wafer is thinned througha process such as grinding in order to expose the conductive vias on thebackside of the wafer. This process of thinning the wafer can damage theedges of the wafer and can make the wafer even more fragile andsusceptible to damage during subsequent transportation and processing ofthe wafer.

To help alleviate these types of damage, a carrier may be attached tothe wafer. Typically, before, this carrier was attached using anadhesive, and was intended to allow handling of the wafer by handlingthe carrier. Additionally, the added strength of the carrier supportsthe wafer so that stresses caused by transportation and/or processingwill not damage the wafer. A typical carrier may be a glass substrateattached to the wafer using an adhesive. It has been found, however,that the wafer may warp during processing and that the typical carrierdoes not provide sufficient support to prevent warping. As a result ofthe warpage of the wafer, processes may fail and/or cause alarmconditions. The first portion of the IC fabrication, where the activetransistors, resistors and RC circuits, and local wiring to interconnectthe transistors are patterned in the semiconductor, is calledfront-end-of-line (FEOL) processing. FEOL processing may also include:well formation; gate module formation; source and drain moduleformation; DRIE (dry reactive ion etch); PVD, Ti or Cu, or other; CVDTiN or other; PECVD SiO2, or other; Electrolytic Cu (or other) Plating;Cu (or other) annealing; Metrology (X-Ray or other); Cu (or other) CMP(Chemical Mechanical Polish); Cu (H2O2+H2SO4)+Ti (DHF) Wet Etch; SputterAdhesion Layer (Ti or other); Sputter Seed Layer (Cu or other);Lithography (Photoresist, expose, strip, etch Cu). Due to some of thehigh temperature (e.g., ≥500° C.,in some instances, 500° C. to 650° C.,and in some cases up to 700° C.) processes associated with FEOLprocessing, many adhesive based solutions cannot be used, as they mayfail to hold the bond, they may outgas contaminants, or both. Manyadhesives even outgas at much lower temperatures, e.g., around 300° C.The portion of IC fabrication line where the coarse wiring that connectslonger distances across individual chip and goes to off chip locationsare interconnected with wiring on the wafer is called back-end-of-line(BEOL) wiring. BEOL processing may also include one or more of formationof contacts, insulating layers, interconnect wiring, RF shielding,passivation, ESD protection, bonding pads and other bonding sites forchip-to-package solutions. Although BEOL processing temperatures aregenerally lower than FEOL processing temperatures, dielectric depositiontypically occurs at 350-450° C. and most adhesives outgas at these lowertemperatures. Moreover, most temporary adhesives have high CTEs whichare mismatched with the wafer and carrier materials, and are difficultto remove while leaving the delicate microstructures on the waferintact. Additionally, the CTE mismatch between the adhesive and thewafer and/or carrier materials may cause undesirable warping of thewafer. Still further, adhesive may find its way into the vias of aninterposer when bonding to a carrier and undesirably preventmetallization of at least part of the via.

Thus, there is a need for an improved carrier-substrate solution thatcan withstand processing conditions, particularly the high temperaturedemands of FEOL processing. Additionally, a carrier-substrate solutionthat can withstand the rigors of FEOL, and yet provide for easydebonding thereafter, will allow a thinner initial substrate to be usedfrom the get-go, thereby alleviating the need for back-end thinning.That is, typical existing semiconductor tools are designed to processwafers on the order of 500 microns and above. However, with a carriersupporting a wafer, the combined thickness need only be within thetools' processing thickness range. Thus, for example, a carrier having athickness of 400 microns may be used to support a wafer of 100 microns,and the combination processed in the existing semiconductor tool. Withthe present solution, due to the controlled bonding that allows easyseparation even after high temperature processing, 100 micron wafers maybe used as substrates, thereby avoiding the waste and potential yieldreductions of thinning after forming devices on the wafer. The abilityto withstand FEOL processing will allow a carrier-substrate solution tostart with a wafer having a thickness of ≤200 microns, for example, 200,190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50,40, 30, or 20 microns. The wafer of such a thickness (≤200 microns forexample) can be attached to a carrier, processed, and then removed fromthe carrier. This can be a major advantage when, for example,polysilicon or single crystal silicon wafers are used as the substratesbecause there can be avoided the removal and waste of a very expensivematerial; the material can simply be processed at its as-formedthickness.

Additionally, 3D IC technology has been widely accepted by theSemiconductor Industry as a major technology trend to improveperformance of semiconductors without requiring ever more expensiveadvanced lithography solutions or requiring larger chip size toaccommodate more circuitry. This technology for 3D ICs relies on thinnedsilicon ICs, and also on interposers to redistribute electrical signalsbetween IC's directly on a single interposer in a planar configuration(2.5D IC) as well as to stack thinned IC's (3D IC).

These interposers, which can be made of polysilicon, single crystalsilicon or glass, allow dramatic improvements in the speed ofcommunications by reducing path lengths from millimeters to microns. Thelead application for this new technology has been Field ProgrammableGate Arrays (FPGA), a high end specialized functionality manufactured byXilinx (San Jose, Calif., USA), for example.

Interposers are characteristically on the order of 50 um to 100 umthick, sized from 200 mm OD to 300 mm OD today, trending towards largersized panels long term. The vias, through which electrical signals areprocessed following metallization, are from 5 um OD to 150 um OD with adensity typically 1 to 20 vias per square millimeter, depending ondesign and application. Interposers are by definition thin, as thickinterposers cause an unacceptable form factor (height) and performance(heat) obstacles. Thin is generally regarded as around 100 microns, butgenerally not to exceed 200 microns. On the other end, the InternationalTechnology Roadmap for Semiconductors (ITRS) allows for thicknesses downto 50 um. Again, substrates of these thicknesses generally cannot beprocessed in existing tools. Thus, the present disclosure contemplatesthe advantageous use of a carrier, and one that may stay attached withthe wafer even during high temperature processing, and yet still allowan easy release of the wafer after such processing.

Although the interposer technology is new, the dominant interposersubstrate is single crystal silicon, with glass emerging as analternative. The attractiveness of glass is performance and cost, but nosolution has yet existed today to realize these advantages for glass.The concepts in the present disclosure will allow processing of avariety of thin substrates as wafers, including silicon and glass, aswell as under a variety of conditions, including FEOL and BEOL, toprovide a variety of devices including ICs, RC circuits, andinterposers.

The bonding solutions of the present disclosure allow the processing ofthin form at final thickness glass, as well as thinned Silicon, throughall existing required process steps with high yield and with lowprocessing time. After the thin wafer is processed throughmetallization, distribution layer placement, it can be debonded leavingthe thinned and processed interposer, and/or IC, intact. Moreover, theuse of carrier with an already-thinned (on the order of ≤200 microns)silicon wafer allows the wafer to be screened before any devices areprocessed thereon. Accordingly, costs can be reduced and/or yieldsimproved.

In light of the above, there is a need for a thin sheet—carrier articlethat can withstand the rigors of the FEOL processing, including hightemperature processing (without outgassing that would be incompatiblewith the semiconductor or display making processes in which it will beused), yet allow the entire area of the thin sheet to be removed (eitherall at once, or in sections) from the carrier. The present specificationdescribes surface treatments to control the adhesion between the carrierand thin sheet to create a temporary bond sufficiently strong to surviveFEOL processing (including high temperature processing) but weak enoughto permit debonding of the sheet from the carrier, even afterhigh-temperature processing. More specifically, the present disclosureprovides surface treatments that may be provided on the thin sheet, thecarrier, or both, to control both room-temperature van der Waals, and/orhydrogen, bonding and high temperature covalent bonding between the thinsheet and carrier. Even more specifically, the room-temperature bondingmay be controlled so as to be sufficient to hold the thin sheet andcarrier together during vacuum processing, wet processing, and/orultrasonic cleaning processing. And at the same time, the hightemperature covalent bonding may be controlled so as to prevent apermanent bond between the thin sheet and carrier during hightemperature processing, as well as maintain a sufficient bond to preventdelamination during high temperature processing.

Another use of the surface treatments, which form the temporary bondingcondition, is to provide for use of a thin sheet on a carrier to processthe thin sheet in processes requiring a temperature ≥400° C. (forexample ≥450° C., ≥500° C., ≥550° C., ≥600° C.), as in FEOL processing,for example. That is, the thin sheet may be a wafer that is processed atthickness without having to thin it later on. Surface treatments asdescribed herein may be used to provide reuse of the carrier under suchtemperature conditions. Specifically, these surface treatments may beused to form a temporary bond between the thin sheet and carrier,whereby the entire thin sheet may be separated from the carrier afterprocessing. The thin sheet may be separated all at once, or may beseparated in sections as, for example, when first removing devicesproduced on portions of the thin sheet and thereafter removing anyremaining portions to clean the carrier for reuse, for example. In theevent that the entire thin sheet is removed from the carrier, as byremoval of the thin sheet as a whole, or as by removing diced sectionsof the thin sheet the sum of which add to the entire thin sheet, thecarrier can be reused as is by simply by placing another thin sheetthereon. Alternatively, the carrier may be cleaned and once againprepared to carry a thin sheet by forming a surface treatment anew.Because the surface treatments provide a temporary bond between the thinsheet and the carrier, they may be used for processes whereintemperatures are ≥600° C. Of course, although these surface treatmentsmay control bonding surface energy during processing at temperatures≥600° C., they may also be used to produce a thin sheet and carriercombination that will withstand processing at lower temperatures, forexample temperatures ≥400° C. (for example ≥450° C., ≥500° C., ≥550°C.), and may be used in such lower temperature applications to controlbonding, for example in BEOL processing. The thin sheet may be apolysilicon or single crystal silicon wafer, silicon wafer, glass,ceramic, glass-ceramic, quartz, sapphire, having a thickness of ≤200microns, and may be processed at, for example temperatures ≥500° C. toform RC circuits, ICs, or other electronic devices thereon in FEOLprocessing. After FEOL processing, the wafer may easily be removed fromthe carrier without damaging the electronic devices. Before removal,however, the wafer may undergo further, lower temperature processing, asin BEOL processing, for example.

A second use of the surface treatments, to provide a temporary bond, isto fabricate an interposer. In this case, the thin sheet is aninterposer, which may be a wafer made from any suitable materialincluding silicon, polysilicon, single crystal silicon, glass, ceramic,glass-ceramic, quartz, sapphire, for example, and which may have athickness of ≤200 microns, for example.

An example of an interposer, and the fabrication thereof, will now bedescribed with reference to FIGS. 6-8.

With reference to FIG. 6, a thin sheet 20 may be bonded to a carrier 10by a controlled bonding area 40, i.e., an area in which a temporary bondis formed between the thin sheet 20 and the carrier 10.

In this embodiment, the carrier 10, may be a glass substrate, or anothersuitable material having a similar surface energy as glass, for example,silicon, polysilicon, single crystal silicon, ceramic, glass-ceramic,sapphire, or quartz. An advantage of using a glass substrate is thatflat sheets having minimal thickness variation can be obtained at arelatively low cost, avoiding the need for expensive carrier substrates.Additionally, with glass, a high quality can be achieved in a costeffective manner. That is, a very uniform thickness glass substrate canbe made very cheaply, and used as a carrier. However, with the surfacetreatments of the present disclosure, the carrier need not be a highprecision carrier having a low total thickness variation as in the casewhere the wafer will be thinned to final thickness. That is, when awafer on a carrier will be thinned, the carrier must have a very tightcontrol on total thickness variation because any variation in thecarrier will be present in the thinned wafer upon thinning. With thesurface treatments of the present disclosure, which allow formingdevices on the wafer when the wafer is already at final thickness, thetotal thickness variation of the carrier is much less important.

In this embodiment, the thin sheet 20 is used to form interposers 56.The sheet may be silicon, including polysilicon or a single crystalsilicon wafer, quartz, sapphire, ceramic, or glass, for example. Thesheet 20 may have a thickness of ≤200 microns. The interposers 56 eachhaving a perimeter 52 and an array 50 of vias, wherein the array 50 hasa perimeter 57. Although ten interposers 56 are shown, any suitablenumber—including one—may be disposed on one thin sheet 20. Forconvenience of illustration, each interposer 56 is shown as having onlyone array 50 of vias, but such need not be the case; instead anyinterposer 56 may have more than one array 50. Further, although eachinterposer is shown as having the same number of arrays 50, such neednot be the case; any number (including zero) of the interposers may havethe same number of arrays 50. Additionally, although the arrays 50 willtypically have the same number and pattern of vias, such need not be thecase. For convenience of illustration, vias 60 are shown on only one ofthe arrays 50 of one of the interposers 56, but such need not be thecase, i.e., any one or more of the remaining interposers 56 may have oneor more arrays 50 of vias 60.

Reference will now be made to FIG. 7, which is a cross-sectional view astaken along line 7-7 in FIG. 6. The vias 60 may include through vias orblind vias, i.e., vias that end within the thickness of the sheet 20.Vias 60 have a diameter 62, and are spaced at a pitch 64. Although thediameters 62 are shown as being the same, such need not be the case,i.e., there may be different diameter vias in one array 50 or indifferent arrays 50 on one interposer 56. The diameter 62 may be from 5microns to 150 microns, for example. Similarly, although the vias 62 arespaced at the same pitch 64, such need not be the case, i.e., differentpitches may be present in one array 50, or in different arrays 50 on oneinterposer 56 or in different interposers 56 on one thin sheet 20. Thepitch may be such that there are from 1 to 20 vias per squaremillimeter, for example, and will depend upon the design and applicationof the interposer. Additionally, material 61 may be present in any oneor more of the vias 60. The material 61 may be an electricallyconductive material, an electrically insulating material, or acombination thereof. For example, a conductive material may be formed onthe perimeter of the via, i.e., at its outside diameter 62, and either adifferent conductive material or an insulating material may be used tofill in the remainder of the via.

Reference will now be made to FIG. 8, which is a view similar to that inFIG. 7, but with devices/structures disposed on the interposer 56 andconnected to via(s) 60. As shown in FIG. 8, a device 66 may be disposedover, and connected with, a plurality of vias 60. Device 66 may includeintegrated circuits; MEMS; microsensors; power semiconductors;light-emitting diodes; photonic circuits; CPU; SRAM; DRAM, eDRAM; ROM,EEPROM; flash memory; interposers; embedded passive devices; andmicrodevices fabricated on or from silicon, silicon-germanium, galliumarsenide, and gallium nitride. Although only one device 66 is shown,there may be any suitable number of devices 66 on one interposer 56,including an array of devices 56. Alternatively, a structure 68 may bedisposed over and connected with only one via 60. Structures 68 mayinclude: solder bumps; metal posts; metal pillars; interconnectionroutings; interconnect lines; insulating oxide layers; and structuresformed from a material selected from the group consisting of silicon,polysilicon, silicon dioxide, silicon (oxy)nitride, metal (for example,Cu, Al, W), low k dielectrics, polymer dielectrics, metal nitrides, andmetal silicides. Although only one structure 68 is shown, there may beany suitable number of structures 68 on one interposer 56, includingarray(s) of structures 56. Further, one or more structures 68 may bedisposed on a device 66.

In the controlled bonding area 40, the carrier 10 and thin sheet 20 arebonded to one another so that over the entire area of overlap, thecarrier 10 and thin sheet 20 are connected, but may be separated fromone another, even after high temperature processing, e.g. processing attemperatures ≥400° C., for example ≥450° C., ≥500° C., ≥550° C., ≥600°C., and on up to about 650° C., or in some cases to 700° C.

The surface treatments disclosed herein result in an interfacial bondinglayer 30 to provide temporary bonding areas 40 between the carrier 10and the thin sheet 20. Specifically, these surface treatments may beformed within the perimeters 52 of the arrays 50 either on the carrier10 or on the thin sheet 20. Accordingly, when the article 2 is processedat high temperature during device processing, there can be provided atemporary bond between the carrier 10 and the thin sheet 20 within theareas bounded by perimeters 52 whereby a separation force may separate(without catastrophic damage to the thin sheet or carrier) the thinsheet and carrier in this region, yet the thin sheet and carrier willnot delaminate during processing, including ultrasonic processing.Additionally, because of the very small thickness of the interfacialbonding layer 30, i.e., less than 100 nanometers, less than 40nanometers, less than 10 nanometers, and in some instances about 2nanometers, there is no effect on the wafer due to CTE mismatch betweenthe wafer and the surface treatment (as there is in the case of thickeradhesive layers, i.e., on the order of 40-60 microns or more).

Then, during extraction of the interposers 56 (each having an array 50of vias 60) having perimeters 52, the portions of thin sheet 20 withinthe perimeters 52 may simply be separated from the carrier 10 afterprocessing and after separation of the thin sheet along perimeters 52.Alternatively, the thin sheet 20 (and alternatively both the thin sheet20 and the carrier 10) may be diced along lines 5, whereby a section ofthe thin sheet 20 larger than the interposer 56 perimeter 52 may beremoved from the carrier 10, or sections of the carrier 10 as in theevent that the carrier is diced together with the thin sheet 20. Becausethe surface treatments provide temporary bonding of the thin sheet withthe carrier, they may be used for processes wherein temperatures are≥600° C. Of course, although these surface treatments may controlbonding surface energy during processing at temperatures ≤600° C., theymay also be used to produce a thin sheet and carrier combination thatwill withstand processing at lower temperatures for example ≥400° C.(for example ≥450° C., ≥500° C., ≥550° C.), and may be used in suchlower temperature applications.

In embodiments, the sheet 20 comprises silicon, quartz, sapphire,ceramic, or glass.

In embodiments, the sheet 20 thickness is ≥200 microns.

In embodiments, the sheet 20 further comprises at least one via therein.In embodiments, the at least one via has a diameter of ≥150 microns. Inembodiments, the at least one via may comprise electrically conductivematerial therein.

In embodiments, the sheet 20 comprises a device surface opposite thesurface temporarily bonded to the carrier 10, the device surfacecomprising an array of devices selected from the group consisting of:integrated circuits; MEMS; CPU; microsensors; power semiconductors;light-emitting diodes; photonic circuits; interposers; embedded passivedevices; and microdevices fabricated on or from silicon,silicon-germanium, gallium arsenide, and gallium nitride.

In embodiments, the sheet 20 comprises a device surface opposite thesurface temporarily bonded to the carrier 10, the device surfacecomprising at least one structure selected from the group consisting of:solder bumps; metal posts; metal pillars; interconnection routings;interconnect lines; insulating oxide layers; and structures formed froma material selected from the group consisting of silicon, polysilicon,silicon dioxide, silicon (oxy)nitride, metal, low k dielectrics, polymerdielectrics, metal nitrides, and metal silicides.

In embodiments, the interfacial bonding layer 30 is from 0.1 to 100 nmthick.

In embodiments, the carrier and the sheet are temporarily bonded over anarea of ≥100 square cm.

In embodiments, the sheet 20 and carrier 10 temporarily bonded togetherare subject to FEOL processing. In embodiments, the FEOL processingcomprises processing-chamber temperatures of from 500° C. to 700° C. Inembodiments, the FEOL processing comprises at least one of: DRIE (dryreactive ion etch); PVD; CVD TiN; PECVD SiO2; Electrolytic Cu Plating;Cu Annealing; Metrology; Cu CMP; Cu (H2O2+H2SO4)+Ti (DHF) Wet Etch;Sputter Adhesion Layer; Sputter Seed Layer; Lithography (Photoresist,expose, strip, etch Cu).

EXAMPLES

The following Examples demonstrate making, use, and analysis of thedisclosed laminate glass products in accordance with the above generalprocedures. The following Examples also demonstrate an ability tocontrol the resulting strength of the interfacial bond between thecomponent pieces in the laminate article.

Example 1

Carrier Cleaning The carrier can be cleaned prior to use in thedisclosed process, after use in the disclosed process followingdebonding or separation of the glass work piece, or both. The cleaningstep can include, for example, one or more of: DI water rinse,NH₄OH:H₂O₂:H₂O mixture, O₂ plasma treatment, an acid rinse (i.e., HCl orHCl:H₂O₂) and like rinses, or a combination thereof. The cleaning stepis primarily concerned with significantly minimizing the density ofparticles on the cleaned surface.

Example 2

Surface Treatment In an additive surface treatment process of thedisclosure, the surface of the carrier or the glass work piece can bemodified to permit van der Waal bonding while eliminating or minimizingcovalent bonding. The treated surface provides adhesive stabilitybetween the carrier and the work piece up to moderate processtemperatures (e.g., 600° C.). The surface treatment can be accomplishedwith a fluorine plasma having process conditions of, for example, avacuum pressure of 50 mTorr, a reactant flow rate and concentration of25 sccm CHF₃ and 25 sccm CF₄, a 200W RF power, and a 60 second fluorineplasma exposure or treatment time. Alternatively, a similar surface maybe prepared in an ICP plasma configuration with CF₄ as the etchant andC₄F₈ as the fluoropolymer former, or in an RIE chamber with CF₄ as theetchant and CH₄ as the fluoropolymer former, or in an RIE chamber withCF₄ as the etchant and H₂ as the polymer former.

In another example, the counterpart work piece to be bonded can be, forexample, a semiconductor substrate or a substrate for epitaxial growth,such as silicon, gallium arsenide, or sapphire. These substrates bond tothe treated carrier glass similar to the thin glass substrate describedabove by either hand bonding or roller lamination. The adhesion of thesesubstrate materials was similar to that of the above glass substrates,both as bonded and after thermal processing.

Example 3

Bonding a thin glass work piece to a carrier substrate. In an examplebonding procedure, a thin glass work piece was lightly contacted with acarrier surface that had been treated with any of the treatments in thepreceding example. Contacting pressure, for example, from a mechanicalsource, or like source, can be applied to one or more points on eitheror both the thin glass work piece and the carrier. The lightly appliedpressure can initiate a bonding wave front.

In another example bonding procedure, the bond can be accomplished by atraditional mechanical lamination method by, for example, applying anuntreated or treated thin glass work piece to a treated carrier with aroller lamination assembly.

Example 4

Device (e.g., Flat Panel Display) Fabrication on the Bonded Thin GlassWork Piece Device processing, that is, creation, fabrication,modification, etc., can be accomplished on the exterior and unboundedsurface of the bonded thin glass work piece using conventional processtechniques such that devices, circuits, or like structural or surfacemodification of the non-bonded thin glass work piece surface occurs.Device processing can include, for example, exposure to acids, bases,vacuum, film deposition, plasma etching, high temperature annealingvacuum, and like processing steps.

Example 5

Debonding Debonding processing permits the bonded thin glass work piece,now having the device processed outer surface, i.e., the device modifiedglass substrate, to be mechanically and relatively easily removed fromthe carrier substrate. Removal from the carrier can be accomplished byany suitable device or method, for example, grabbing a corner usingvacuum suction and pulling on the bonded thin glass work piece to removeit from the carrier by, for example, peeling.

Example 6

XPS method of determining surface composition. X-ray PhotoelectronSpectroscopy (XPS) was used to study and measure the surface compositionand speciation of all surfaces. All XPS data were collected using acommercial XPS instrument (PHI) employing AlKα radiation and a take offangle of 45°. The spectra were analyzed using the software andsensitivity factors provided by the XPS instrument vendor. The followingorbitals were used to determine the surface composition: Si 2p, Al 2p, O1s, C 1s, Mg 2s, Ca 2s, B 1s, F 1s, and Sr 3d. The reportedconcentrations of these elements were averages of concentrations of eachof these elements over the entire probed depth of the XPS signal.

Example 7

Changes in surface composition as a function of CHF₃ (fluoropolymerforming agent) and CF₄ (etchant) ratio Table 1 shows the surface atomicratios of select elements obtained from FIG. 4 (Al:Si, Ca:Si, Mg:Si,Sr:Si) for untreated EXG glass and EXG glass following plasma treatmentin different ratios of CF₄ and CHF₃. The data clearly show that plasmasurface treatment results in substantial increase in the Al:Si, Ca:Si,Mg:Si, and Sr:Si atomic ratios for the treated EXG surfaces as comparedto untreated EXG surface, which results are indicative of the relativedepletion of Si compared to Al, Ca, Mg, and Sr.

TABLE 1 Atomic ratios of selected elements obtained from FIG. 4 comparedwith the same ratios in the surface composition of untreated EXG.CF₄/(CF₄ + CHF₃) Al:Si Ca:Si Mg:Si Sr:Si 0 1.9  1.1  0.3  0.07 (i.e.,100 mol % CHF₃) 0.2 1.9  1.3  0.3  0.08 0.4 2.0  1.5  0.3  0.07 0.6 2.4 1.6  0.4  0.08 0.8 2.5  1.6  0.4  0.10 1 2.4  1.6  0.4  0.10 (i.e., 100mol % CF₄) EXG no 0.26 0.10 0.01 0.01 treatment control

The presence of a carbonaceous overlayer is known to affect the atomicratios of the underlying elements due to selective attenuation of XPSsignal originating from different orbitals. In the ratio of Ca:Si, thechanges due to measurement artifact is small and in the ratios of Al:Si,Mg:Si, and Sr:Si, these changes are minimal and essentially belowdetection limits.

Example 8

Determination of Formation of Fluoride Species on Glass Surface XPS wasalso used to perform speciation of fluorine detected on the surfaces.The F is spectra could be peak fitted with two distinct peaks separatedby about 1.9 eV. The lower binding energy peak was assigned to fluorinepresent as metal fluoride species while the higher binding energy peakwas assigned to fluorine in reaction with the carbonaceous layer. Inthis manner it is possible to obtain the fraction of fluorineconcentration detected on the surface by XPS which is due to metalfluorides and the fraction of fluorine present in the fluoropolymerlayer.

Knowing the concentration of fluorine that is in the form of metalfluorides, and knowing the total concentration of cations detected byXPS, it is possible to calculate the total fluorine to cation ratio. Inthis instance, total cation concentration is defined as the totalconcentrations of B, Al, Mg, Sr, Si, and Ca as detected by XPS underconditions defined in Example 7. The results of such analysis for theexamples of pure CHF₃ and pure CF₄ plasma conditions are presented inTable 2.

The results in Table 2 indicate that for the example of pure CHF₃ amajority of fluorine concentration detected by XPS on the surface is inthe form of fluoropolymer while in the example of pure CF4, a minorityof the fluorine concentration detected by XPS is in the form offluoropolymer.

TABLE 2 Total concentration of fluorine detected on the surface, thetotal portion of fluorine present as metal fluorides, and the fluorineto glass cations ratios for pure CHF₃ or pure CF₄ plasma compositions.50 sccm CHF₃ 50 mTorr 50 sccm CF₄ 50 mTorr total F as total F as Totalmetal F:cation Total metal F:cation time surface F fluoride ratio forsurface F fluorides ratio for (sec) (at %) (at %) glass (at %) (at %)glass 60 48.5 14.2 2.2 52.4 50.9 2.3

The disclosure has been described with reference to various specificembodiments and techniques. However, it should be understood that manyvariations and modifications are possible while remaining within thescope of the disclosure.

What is claimed is:
 1. A laminate glass article, comprising: a glassdevice substrate bonded to a glass carrier substrate with at least oneinterfacial bonded surface that has been treated with a plasma selectedfrom: a fluoropolymer; the reaction products of a fluorinated etchingagent; or a combination thereof, wherein the interfacial bond strengthbetween the glass device substrate and the glass carrier substrate isfrom about 100 to about 1,000 mJ/m², the interface between the glassdevice substrate and the glass carrier substrate has a silicon contentof from about 0.1 to about 14 at %; a fluorine content of from about 5to 65 at %, and a metal to fluorine (M:F) atomic ratio of about 1:1 to1:3.
 2. The article of claim 1 wherein the glass device substrate has athickness of from about 20 to about 500 microns, the glass carriersubstrate has a thickness of about 200 micron to about 3 mm, and thethickness of the interfacial bonding layer between the glass devicesubstrate and the glass carrier substrate is from about a single atomiclayer to about 100 nanometer.
 3. The article of claim 1 furthercomprising the non-bonded second surface of the glass device substratein the laminate article has at least one device modified surface area.4. The article of claim 1 wherein the glass device substrate has aplurality of holes therein.